Anthraquinone-acridone derivatives and process of preparing the same



UN HTED T TE AT 35 acridone compounds in which the imide group 1 ingused as dyestui'r'svby-themselves' and are furimino-radicles, such asaroyl-imino or 1,2-benznated as 1 ,2. Among the various possibleresidues Patented Aug. 7, 1934 13 9 2162 N rf' o'er! c E ANTHRAQUINONE:aoainomi DERIVATIVES .annraocnss oFPREPARrNG THE SAME 7 Ivan Gubelmann,South Milwaukee, and William Dettwyler, Milwaukee, Wis, assignors, by'me'sne ass gnments, 150E. I." (in Pent de Nemours & Company, acorporation of Delaware No Drawing.- Application -August13g1931,

SeriaI -No. 556,938 I n ean, 1 west ,This invention relates to novelorganic com--. pounds of the anthraquinone 'acridone series, and aprocess of preparing the same. It is an object of this invention toprepare novel anthrimidee and the heterooyclic ring are attached todiffer: ent benzene nuclei of the same anthraquinone residue. We havefound that anthrimide-acridone compounds ofthis type are capable ofbether valuable as intermediates for other dyestuifs.

The novel compounds with which this invention dealsv in generalpossessthe following nuclear structure:

wherein R stands 'for a radical of the anthraquinone series which may befurther substituted by acridonyl; while (0:) indicates that the groupR,-NH occupies either one of the positions 5 and 8 in theacridonyl-anthraquinone nucleus, the positions of the heterocyclic ringbeing desigrepresented by R, the following may be mentioned:anthraquinonyl, benzoyl-i mino-anthraquinonyl,1,2-benzacridony1-anthraquinonyl,v etc. yu Depending on the selection ofR, therefore, our

40 novel compounds may be illustrated by the following typicalrepresentatives:

(vis-a-vis designating substitution in opposite rings of theanthraquinone nucleus) with a halogen anthraquinone compound of the typeR-X, wherein R. has the same significance as above, while X stands forC1 or Br, in the presence of an amidation catalyst such as 'a coppercompound and suitable acid binding agents. "We may, however, also use asinital materials compounds of the type:

' HN (L I O (a)X-i Example 1 10 parts of8-amino-1,2-anthraquinonerbenzacridone (obtainablejforiinstance byring-closing in known mannensay by the aid of sulfuric or chlorosulfonicacid, 8-amin0-1-ortho-carboxyanilino-anthraquinone, in turn obtainableby reacting 1-chloro-S-amino-anthraquinone with anthranilic acid or asalt thereof by any suitable procedure, for instance by the methoddescribed in British Patent No. 312,678) are added to 100 parts ofnitrobenzene, and 7.5 parts of a-ChlOIO- anthr'aquinone, 4 parts ofsodium carbonate and 0.8 parts of cuprous chloride are added. Themixture is heated to about 200 to 205" C. and

.stirred at this temperature for about 16 hours.

It' is now cooled and poured into 200 parts of water, and thenitrobenzene is distilled off by the aid of a'steam jet. The residualmass is filtered hot, and the filter cake is washed with hot water untilfree of inorganic salts, dried and ground.

The product constitutes a dark violet powder; insoluble in water, diluteacids, or dilute alkalis. It is sparingly soluble in hot nitrobenzene,imparting thereto a purple color. It is readily soluble in concentratedsulfuric acid with a bright, brown color, but precipitates therefromupon dilution with water in the form of 'violetfl'ocks. It is readilysoluble in the usual sodium-'hy'drosulfite vat with a violet color, fromwhich cotton maybe dyed-in violet shades.

The product is most probably S-a-anthraquinonyl-dmino-1,2-anthraquinonebenzacridone, corresponding instructure to Formula (1) above.

Example 2 0.8 parts of-cuprous chloride are added. The rest of theprocedure is the same as in Example 1.

The product is similar .in properties to that obtained in Example 1,except that the colors of the various solutions and the dyeings uponcotton are of somewhat redder shade. It is most probablyfi-a-anthraquinonyliminm1,2-anthraquinone-benzacridone, corresponding instruc ture toFormulalII) above.

Example 3 Example 4 The procedure is the same as in Example 1, exceptthat in lieu of 7 parts of a-chloro-anthraquinone therein specified, anequal weight of c-chloro-anthraquinone is herein used.

The product is similar in :properties to that of Example 1, except thatits color in sulfuric acid is yellow, and itsdyeings upon cotton are amore bluish shade of violet than the dyeings of the product of eitherExample 1 or Example 3. It is 1 dried and ground.

product obtained in Example 3 were suspended I and steam-distilled witha jet of steam until free Wetclalm:

most -Probab1y 8*+anthraquinonylimino--1;2 ane thraqumone-benzacridone';1 "corresponding in 1. An anthrimideeacrido'ne"compound possessstructure to Formula (IV) above. a ing the following nuclear structure:

Example 5 The procedure is the same as in Example 1, except that in lieuof '7 parts of u-chloro-anthr'aquinone therein specified, 11 parts ofl-chloro-S- benzoylamino-anthraquinone are herein used.

The product is a dark powder; insoluble inf water, dilute acids, ordilute alkalis. It is somei what soluble in hot nitrobenzene, impartingi thereto a claret red coloration. It is readily soluble in concentratedsulfuric acid with a redbrown -color, but precipitates therefrom upondilution with water in the form of violet flocks; It dissolves readilyin the usual hydrosulfite vat with a violet jcolor, from which cotton isdyed a violet shade.

The product is'most probably 8-(5'-benzoylamino-1 -anthraquinonylimino)1,2-anthraquinone-benzacridone, corresponding in structure to Formula(V) above;

The products obtained ;in the. aforegoing examples may be halogenated,if desired, to produce the corresponding halogen derivatives.

Exaniple 6 wherein. ,R ,stands for a radical of, theanthraquinoneseries, while (0:) indicates .that -.the-1N I I1 group-isattached :to one of the positions 5' and; 8.,

2. An anthrimide -acridone. compound havingthefollowing'g'eneral'formulazz v I i 10 grams of the dry, pulverizedcondensation in 100 parts of nitrobenzene. 0.1 part of iodine was addedand the mixture was heated to 100 C;l

Chlorine gas was passed in slowly for two hours.

The mass was poured into 200 grams of water,

of nitrobenzene. The residual mass was filtered .i m 111 of it ef b zlei Series, 1 a radical,

and the filter cake was washed with hot water, rtnepy Ff i The productwas a dark violet powder, insoluble in water, dilute acids and dilutealkalis. It is soluble in hot nitrobenzene with a violet coloration. Itdissolves readily in concentrated sulfuric acid, imparting thereto adull red color, but precipitates ther efrom-upo n-dilution with waterinthe formjof reddish-,violet flocks-.; It is readily soluble in theusual sodiumehydrosulfite vat with; aviolet color, and dyes; cottonthere from in reddish violet shades considerably redder y than theinitial material.--: ,l t V Its chlorine content is 35.7%. It willbeunderstood that many. variations are possible in theprocedures aboveset forth withtt 9. 9 t ?l 9 a out departing from the'spirit of this"invention. An P h i if e, mw 'hilin For" instance, instead of the"chloro-derivatives the followmg general formula-3 of the anthraquinonesabovementioned, the cor responding bro'mo-derivatives" -may be used.Homologous or otherwise substituted anthrae i quinone bodies may beused. Instead of starting with a halogen-anthraquinone body and anamino-anthraquirione-acridone body, one may select the correspondingamino-anthraquinone and halogen-anthraquinone-acridone bodies. Manyother variations are possible, as will be readily understood tojthos'eslgilled in the art.

In the above disclosure it should be understood that wherever we are"referring to the dyeing of cotton, we imply'of 'course, the, usualprocedure of dyeing with vat dyestuffs, involving at the end wh in i attha 3 19 2 @Pf an aeration or oxidationpf the dyed material. a h t 99 1P Q 1f f?1 f f In the claims below it should be understood QQ PH WE 1 mdarkms rgmr that where new products, dyestuffs, or articles of S13 9 Qllb m flq 3 89 .9 a d w it manufacture are claimed, we mean to include@lk fl ly so ubl 99n i d 1 u m these bodies not only in substance, butalso in acid With a bright brown 0 1; l egh the whatever state they"exist when applied to mausual alkaline hydrosulfite vat w thavioleticolor, terialdyed, printed, "or pigmented therewith; irom whichcottonmay ped e ip iole h des 150 "wherein R stands for a hydrogenatonii anaroy lno 4. An anthrimide-acridone compound-havingtheiollowingf'general iormula tachdto one ofthe positions dand'gg 's'aidcom 1 pound being in solid" form a; dark 'pow der; in-

soluble in water; dilute acids and dilute alkalis;

readily soluble in concentrated sulfuric acid with a red-brown color;soluble in the usual alkaline hydrosulfite vat with a violet color, fromvwhich cotton may be dyed in violet shades.

wherein (a) indicates 1hat-the NH group is attached to one of the;positions 5 and 8, said compound being in solid form a dark violetpowder; insoluble in water, dilute acids, and dilute alkalis; readilysoluble in concentrated sulfuric acid with a bright brown colorfsolublein the usual alkaline-. 'hyplrosulfite :vat a violet color,;,-from whichcotton may-be dyedmivioletshades,

v An nthrimide acridone: compound possessins the followingnuclearlstructure: 1 v

stands for oi the, anthraquinone serieswhich may be further substitutedby an aroyl-limino group of the'benzene series or bya benzacridone'ring,whilf (oz') indicatesthat the NHgroup isjatta'chd it one prme positionssands; p a. v ""7; process a: producing an anthrimidg acri'd'onecompound, which comprises-"heating in swam:

an inert organfcsliquid in thepresenceoi-an acid absorbing'agent acondensing catalyst a 1,2-

anthraquinonwacridone compound of the general formula: v v

j 3 Q 1 Q EN t and'anahthraquinone body of me general forinula R Y,iwherein R stands for a radical of the anthraquin'one series, one of themembers X'and Y stands for halogen while the other stands for an aminogroup, and wherein (a) indicates that the member X is attached to one01' the positions agThe'proces's" in: producing an anthrimi'deand ananthraqumone body of the formula R--Y, wherein R stands fora radical. ofthe anthraand a chloro-anthraquinone body of the formula:

wherein R stands for a hydrogen atom, a chlorine atom, or abenzoyl-amino group.

10. The process of producing an anthrimideacridone compound, whichcomprises heating in an inert organic liquid in the presence of an acidabsorbing agent and a condensing catalyst a 1,2-

anthraquinone-acridone compound of the general formula:

(or) H2N- wherein (an) indicates that the HzN group is attached to oneof the positions 5 and 8, and a chloro-anthraquinone.

11. The process of producing an anthrimideacridone compound, whichcomprises heating in an inert organic liquid in the presence of an acidabsorbing agent and a condensing catalyst a 1,2- anthraquinone-acridonecompound of the general formula:

wherein (0:) indicates that the HzN group is attached to one of thepositions 5 and 8, and 1,5- dichloro-anthraquinone.

IVAN GUBELMANN. WILLIAM DET'IWYLER.

